Interactions between anions and cations are important to understand the chemical processes of pollutants in environment. In this study, batch experiments were carried out to investigate the simultaneous adsorption of Cu and Cd on hematite as affected by phosphate. Phosphate pretreatment suppressed the maximum adsorption of Cu and Cd on hematite and moved the adsorption pH edges to a higher pH range. Phosphate application time had a marked impact on Cu and Cd adsorption and longer contact time resulted in more reduction of Cu and Cd adsorption. Results of back-titration, Fourier transform infrared (FTIR) spectroscopy study and ionic strength effect on the adsorption revealed that Cu and Cd were adsorbed on hematite mainly through the inner-sphere complex formation mechanism and phosphate treatment reduced the inner-sphere adsorption sites, thus decreasing Cu and Cd adsorption on hematite.